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91.
This study shows the ESR spectra of oxoiron(IV) porphyrin pi-cation radicals of 1-8 in dichloromethane-methanol (5:1) mixture. We reported in a previous paper that oxoiron(IV) porphyrin pi-cation radicals of 1-4 are in an a(1u) radical state while those of 5-8 are in an a(2u) radical. The ESR spectra (g( perpendicular)(eff) approximately 3.1 and g( parallel)(eff) approximately 2.0) for the a(1u) radical complexes, 1-4, appear quite different from those reported previously for the oxoiron(IV) porphyrin pi-cation radical of 5 (g(y) = 4.5, g(x) = 3.6, and g(z) = 1.99). The unique ESR spectra of the a(1u) radical complexes rather resemble those of compound I from Micrococcus lysodeikticus catalase (CAT) and ascorbate peroxidase (ASP). This is the first examples to mimic the ESR spectra of compound I in the enzymes. From spectral analysis based on a spin Hamiltonian containing an exchange interaction, the ESR spectra of 1-4 can be explained as a moderate ferromagnetic state (J/D approximately 0.3) between ferryl S = 1 and the porphyrin pi-cation radical S' = (1)/(2). The magnitudes of zero-field splitting (D) for ferryl iron and isotropic J value, estimated from the temperature-dependence of the half-saturation power of the ESR signals, are approximately 28 and approximately +8 cm(-1), respectively. A change in the electronegativity of the beta-pyrrole substituent hardly changes the ESR spectral feature while that of the meso-substituent slightly does owing to the change in the E/D value. On the basis of the present ESR results, we propose the a(1u) radical state for compound I of CAT and ASP. 相似文献
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Ryota Tsutsumi Tokio Sasaki Chisato Hashiguchi Ryota Yamazaki Syuji Fujii 《Composite Interfaces》2018,25(8):743-760
In order to reinforce the composite consisting of isoprene rubber (IR) and calcium carbonate (CaCO3) particles, the surface treatment of CaCO3 particles with a mixture of amino- and mercapto-functional silane coupling agents was investigated. The quantity of chemisorbed silanes in treated CaCO3 measured using thermogravimetry was greater for amino- than for mercapto-silane and for the tri- than for the dialkoxy structure. Second, the molecular mobility of polycondensate of the mixtures with the trialkoxy structure measured using 1H pulse nuclear magnetic resonance had the least molecular mobility, i.e., formed the highest density network. The greater values of stress at 500% strain, fracture stress, and elongation at break were determined for the treatment with amino- and mercapto-functional silanes having a trialkoxy structure from the stress-strain curves of composite. The mixture treatment with dialkoxy structure and with amino- or mercapto-functional silane only did not improve the mechanical properties sufficiently. Interactions between the amino group and the CaCO3 surface, covalent bonding between the mercapto group and the IR, and high density network formation of trialkoxy silane were important for improving the mechanical properties of the composite. 相似文献
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Nobuyuki Otozawa Rio Hamajima Masataka Yoshioka Raito Kato Arisa Tanaka Hiroto Fukuma Toshiki Terao Kei Manabe Syuji Fujii Yoshinobu Nakamura Atsushi Takahara Tomoyasu Hirai 《Journal of polymer science. Part A, Polymer chemistry》2020,58(14):1960-1964
This study investigates the effect of ionic liquids (ILs) on the anionic polymerization of methyl methacrylate (MMA). Polymethyl methacrylate (PMMA), an isotactic polymer, is prepared by anionic polymerization at a high reaction temperature with an IL that acts as both solvent and additive. The most plausible reaction mechanism is determined using 1H NMR and Fourier-transform infrared spectroscopy. The electrostatic interaction between MMA and the IL increases the apparent steric hindrance in MMA, resulting in the isotactic PMMA. 相似文献
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Yongjoon Kim Prof. Dr. Tomohiro Iwai Prof. Dr. Sho Fujii Prof. Dr. Kosei Ueno Prof. Dr. Masaya Sawamura 《Chemistry (Weinheim an der Bergstrasse, Germany)》2021,27(7):2289-2293
2,2’-Bipyridine ligands (dsbpys) with dumbbell-like shapes and differently substituted triarylmethyl groups at the C5 and C5’ positions showed high ligand performance in the Ni-catalyzed cross-electrophile coupling and the Ni/photoredox-synergistically catalyzed decarboxylative coupling reactions. The superior ligand effects of dsbpys compared to the conventional bpy ligands were attributed to the monochelating nature of dsbpys. 相似文献
100.
Syuji Fujii Shinji Yamashita Yuichi Kakigi Kodai Aono Sho Hamasaki Shin-ichi Yusa Yoshinobu Nakamura 《Colloid and polymer science》2013,291(5):1171-1180
Hydroxy-functional macrodisulfides have been synthesized by atom transfer radical polymerization of 2-hydroxyethyl methacrylate or 2-hydroxypropyl methacrylate in 2-propanol. Mean degrees of polymerization of the polymer chains beside the disulfide were fixed at 30, 60, and 90; since ATRP has reasonably good living character, the molecular weight distribution is relatively narrow. Furthermore, the macrodisulfides were reduced to synthesize corresponding thiol-terminated polymers with relatively narrow molecular weight distributions. 1H nuclear magnetic resonance and gel permeation chromatography were used to characterize the macrodisulfides and thiol-terminated polymers in terms of their chemical structure, molecular weight, and polydispersity, respectively. Dispersion polymerizations of styrene using the thiol-terminated hydroxy-functional polymers as a transtab (chain transfer agent + colloidal stabilizer) in ethanol resulted in colloidally stable submicrometer-sized polystyrene latex particles. Scanning electron microscopy, Fourier transform infrared spectroscopy, and elemental microanalysis were used to characterize the particles in terms of their morphologies, particle sizes and their distributions, and chemical compositions. 相似文献